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RESEARCH ARTICLE

Bulk atmospheric deposition of persistent organic pollutantsand polycyclic aromatic hydrocarbons in Central Europe

Barbora Nežiková1 & Céline Degrendele1 & Pavel Čupr1 & Philipp Hohenblum2 & Wolfgang Moche2 & Roman Prokeš1 &Lenka Vaňková1 & Petr Kukučka1 & Jakub Martiník1 & Ondřej Audy1 & Petra Přibylová1 & Ivan Holoubek1 & Peter Weiss2 &Jana Klánová1 & Gerhard Lammel1,3

Received: 5 February 2019 /Accepted: 14 May 2019 /Published online: 14 June 2019# The Author(s) 2019

AbstractPolycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are ubiq-uitous and toxic contaminants. Their atmospheric deposition fluxes on the regional scale were quantified based on simultaneoussampling during 1 to 5 years at 1 to 6 background/rural sites in the Czech Republic and Austria. The samples were extracted andanalysed by means of gas chromatography coupled to mass spectrometry. For all seasons and sites, total deposition fluxes forΣ15PAHs ranged 23–1100 ng m

−2 d−1, while those for Σ6PCBs and Σ12OCPs ranged 64–4400 and 410–7800 pg m−2 d−1,respectively. Fluoranthene and pyrene were the main contributors to the PAH deposition fluxes, accounting on average for 19%each, while deposition fluxes of PCBs and OCPs were dominated by PCB153 (26%) and γ-hexachlorobenzene (30%), respec-tively. The highest deposition flux of Σ15PAHs was generally found in spring, while no seasonality was found for PCBdeposition. For deposition fluxes forΣ12OCPs, no clear spatial trend was found, confirming the perception of long-lived regionalpollutants. Although most OCPs and PCBs hardly partition to the particulate phase in ambient air, on average, 42% of theirdeposition fluxes were found on filters, confirming the perception that particle deposition is more efficient than dry gaseousdeposition. Due to methodological constraints, fluxes derived from bulk deposition samplers should be understood as lowerestimates, in particular with regard to those substances which in ambient aerosols mostly partition to the particulate phase.

Keywords Bulk atmospheric deposition . POPs . PCBs . OCPs . PAHs . Central Europe . Deposition fluxes

Introduction

Polycyclic aromatic hydrocarbons (PAHs) and many haloge-nated substances, such as polychlorinated biphenyls (PCBs)and organochlorine pesticides (OCPs), are ubiquitous

contaminants in the global environment (UNEP 2003).PCBs and OCPs are bioaccumulative and persistent in envi-ronmental compartments. Moreover, PCBs, many OCPs andmany PAHs are known for their toxic properties, as somecompounds in these groups are possibly carcinogenic, muta-genic and teratogenic (Ali et al. 2014; Bansal and Kim 2015;Ludewig and Robertson 2013; Ross 2004). For example,benzo[a]pyrene (BAP) has been classified as carcinogen forhumans (group 1), while other PAHs were classified as prob-able or possible carcinogens (group 2A or 2B) by theInternational Agency for Research on Cancer (IARC 2010)and are ecotoxic. Most of these substances are now regulatedunder the auspices of international conventions for the protec-tion of the environment and human health (UNEP 2008;UNECE 1999).

PAHs are products of incomplete combustion and haveboth anthropogenic (e.g. traffic, domestic heating) and naturalsources (e.g. crude oil and wild fires) (Dat and Chang 2017).PCBs were widely used as dielectric fluids, plasticisers and

Responsible editor: Philippe Garrigues

Electronic supplementary material The online version of this article(https://doi.org/10.1007/s11356-019-05464-9) contains supplementarymaterial, which is available to authorized users.

* Gerhard [email protected]

1 Research Centre for Toxic Compounds in the Environment, MasarykUniversity, Brno, Czech Republic

2 Umweltbundesamt, Wien, Austria3 Multiphase Chemistry Department, Max Planck Institute for

Chemistry, Mainz, Germany

Environmental Science and Pollution Research (2019) 26:23429–23441https://doi.org/10.1007/s11356-019-05464-9

http://crossmark.crossref.org/dialog/?doi=10.1007/s11356-019-05464-9&domain=pdfhttp://orcid.org/0000-0003-2313-0628https://doi.org/10.1007/s11356-019-05464-9mailto:[email protected]

adhesives from 1930s to 1970s (Backe et al. 2002). InCzechoslovakia, the production ended in the year 1984(Christan and Janse 2005). OCPs were used in agriculturefrom the middle of the last century and dichlorodiphenyltri-chloroethane (DDT) as vector control combatting malaria intropical countries (el Shahawi et al. 2010).

Persistent organic pollutants (POPs) and PAHs can befound in every compartment of the environment and theirphysical and chemical characteristics allow them to betransported from one compartment to another (Cetin et al.2017; Karacik et al. 2013). As semi-volatile organic com-pounds (SOCs), they are partitioning in the atmosphere be-tween the gaseous and particulate phases. This partitioning isone of the most important factors influencing the fate in theatmosphere of these SOCs (Bidleman 1988; Keyte et al.2013), and therefore their long-range transport potential.

Exposure of ecosystems to pollutants is dominated by at-mospheric depositions, dry and wet. Dry deposition is drivenby gravity force and diffusion (Bidleman 1988), while wetdeposition is controlled by precipitation rate and intensity(Atlas and Giam 1988; Castro-Jiménez et al. 2015; Staelenset al. 2005). It has been shown that snow is more efficientlyscavenging than rain (Lei andWania 2004;Wania et al. 1998).The effect of forests on deposition into ecosystems was stud-ied, indicating the strong influences of the surface roughness,climate parameters (e.g. wind velocity) and physicochemicalproperties of the substance (e.g. the octanol/air partition coef-ficient, Koa) (McLachlan and Horstmann 1998; Nizzetto et al.2006; Foan et al. 2012).

Efforts have been made over the last decades to quantifydeposition fluxes for various SOCs. Fluxes for large areas oren t i r e r eg i on s h ave be en e s t ima t e d b a s ed onmulticompartmental modelling (Lammel and Stemmler2012; Scheringer et al. 2004; Stemmler and Lammel 2012)and based on freshwater sediment pollution (Meijer et al.2006). It is important to verify the modelling results by directmeasurements of atmospheric deposition. There are somestudies carried out in quantifying bulk atmospheric depositionof PAHs, PCBs and OCPs experimentally in Europe (e.g.Arellano et al. 2015; Brorström-Lundén et al. 1994; Carreraet al. 2002; Jakobi et al. 2015), while additional data are avail-able for other regions, for example the USA (Schifman andBoving 2015), China (Feng et al. 2017) and the global oceans(González-Gaya et al. 2016). Moreover, additional data forwet deposition and washout ratios are available for Europe(Shahpoury et al. 2015; Škrdlíková et al. 2011).

In previous studies, the seasonal variations of bulk deposi-tion fluxes of PAHs have been characterised, generally show-ing higher deposition fluxes in winter (Binici et al. 2014;Birgül et al. 2011; Blanchard et al. 2007; Gocht et al. 2007).Seasonal variations of PCBs have also been studied but noclear trend has been observed (Agrell et al. 2002; Blanchardet al. 2007; Brorström-Lundén et al. 1994; Carrera et al. 2002;

Newton et al. 2014; Teil et al. 2004). Concerning OCPs, onlyfew studies exist, mainly on the isomers of hexachlorocyclo-hexane (HCH) (Brorström-Lundén et al. 1994; Carrera et al.2002; Jakobi et al. 2015; Teil et al. 2004), while the seasonal-ity of OCP atmospheric deposition has not been addressed yetin these studies.

The aim of this study is to provide novel data on atmo-spheric deposition of PAHs, PCBs and OCPs in CentralEurope. In particular, the seasonal and spatial variations ofthese deposition fluxes were investigated at different rural/background sites along the Czech-Austrian border in 2011–2015.

Material and methods

Sampling

Total (wet and dry i.e. bulk) deposition samples were simul-taneously collected near the Czech–Austrian border at threesites in the Czech Republic, Kuchařovice (KUC), Košetice(KOS) and Churáňov (CHU), and at three sites in Austria,Wolkersdorf (WOL), Unterbergern (UNT) and Grünbach(GRU). All sites are considered as background with limitedanthropogenic sources with the exception of KUC. KUC is arural site, located in the vicinity of agricultural fields and af-fected by emissions from residential area (e.g. domesticheating) located near the sampling site (around 100 m). Amap of the sampling sites is provided in Figure S1 in theSupplementary Material.

From September 2011 to August 2012, deposition sam-plers were deployed at each site. Additional deposition sam-ples were also collected at the same three Czech sites during2012–2015. Exact sampling periods are provided in theTable S1.

The deposition sampler used (Čupr and Pěnkava 2012)consists of a collection vessel (250 mm diameter) made ofborosilicate glass, with a stainless steel particulate filter holderlocated at the bottom of the collection vessel. A glass columncontainingXAD-2 sorbent (Supelco, USA) is connected to thebase of the filter holder and stored in a housing with a mod-erate heater (Figure S2). The sampler is based on the samplerdeveloped for and successfully applied in the MONARPOPproject (Offenthaler et al. 2009; Jakobi et al. 2015). Both sam-plers are a modification of an earlier design (DIN 2002), im-proving sampling efficiency and making sure that exclusivelyinert materials are in contact with the sample. This new designis patented (Čupr and Pěnkava 2012). The XAD resin waspre-cleaned in Soxhlet extractor for 8 h in acetone and 8 h indichloromethane (DCM), dried overnight and stored at roomtemperature. The moderate heater was used only when theambient temperature was lower than 4 °C to prevent the for-mation of ice and to ensure that snowfall is melted

23430 Environ Sci Pollut Res (2019) 26:23429–23441

immediately, such that SOC deposition with snowfall is col-lected and not lost. Therefore, this sampler allows for thesimultaneous collection of dry deposited particulate matterand gaseous compounds as well as the wet deposition.Atmospheric particles were collected on a glass microfibrefilter (GFF, 70 mm, Whatman, USA) and the dissolved phasewas collected on XAD. The sampling duration was about 3months at each site. From 2013 onwards, GFFs were changedevery month. One to three months is the common range oftotal deposition sampling of POPs (Bergknut et al. 2011;Gocht et al. 2007; Jakobi et al. 2015; Newton et al. 2014).After sampling, all samples were wrapped in aluminium foiland plastic zip lock bags and stored at − 18° C until analysis.

Given the low deposition rates and analytical challengesof SOCs, a sampling period of 3 months is appropriate (e.g.Jakobi et al. 2015). Possible sampling artefacts arephotodegradation (photolysis, ozonation), blowoff of depos-ited particles from the surface (McLachlan 1998) andvolatilisation from sampler surfaces (funnel, GFF). The frac-tion of pollutants dissolved by rainwater (or snow melt) isnot subject to volatilisation, but irreversibly trapped in XAD.It had been evaluated using a similar sampler design (funnel,resin cartridge downstream) that up to 10% of the organicscontained in the rainwater is not retained by the sampler, butsubject to breakthrough (McLachlan and Horstmann 1998)and that up to 10% of polychlorinated dibenzo-p-dioxinsand -furans present on the surface of the sampler can be lostif the surface is not rinsed after sampling (Horstmann andMcLachlan 1997). Similarly, a previous study (funnel, filterand resin cartridge downstream; Franz et al. 1991) hasshown that 25–28% of PAHs and 26–62% of PCBsremained on the different parts of the sampler after sampling(i.e. surface, deposition walls) and could be obtained byrinsing the surface. No rinsing was done in this study.Furthermore, because of the significance of surface rough-ness (McLachlan and Horstmann 1998; Pryor et al. 2007;Glüge et al. 2015), dry particle deposition to artificial sur-faces is less efficient than to natural surfaces. Consequently,such type of samplers may underestimate the total flux ofthe target compounds to terrestrial ecosystems. Nevertheless,various advantages of such type of deposition samplingshould be emphasised: comparable sampling across sitesand seasons and, particularly, including SOC deposition re-lated to snowfall, and rather low maintenance of device.

Sample preparation and analysis

GFFs and XAD samples were extracted with DCM using anautomatic extractor (Büchi Extraction System, B-811,Switzerland). Surrogate recovery standards (i.e. D8-naphtha-lene, D10-phenanthrene, D12-perylene, Supelco, Merck,Germany; PCB30 and PCB185, Ultra Scientific, USA) werespiked onto each GFF and XAD before extraction. The

extracts were then concentrated using a gentle nitrogenstream. In 2011–2012, one sampler was dedicated to PAHanalysis while the second one was for PCBs and OCPs. Forthe remaining years, PAHs, PCBs and OCPs were analysedfrom a single deposition sampler and the extracts were dividedwith 10% used for PAHs and the remaining for PCBs andOCPs. PAHs extracts were transferred to a silica columnconsisting of 1 g of anhydrous sodium sulphate and 5 g ofactivated silica and were eluted with 10 mL of n-hexane and20 mL of DCM. Both fractions were collected in the samevial. PCBs and OCPs extracts were transferred to a glass col-umn consisting of 1 g of anhydrous sodium sulphate, 0.5 g ofactivated silica, 8 g of H2SO4-modified activated silica and 1 gof activated silica and were eluted with 30 mL of DCM:n-hexane (1:1).

The PAHs were analysed using gas chromatography 6890GC (Agilent Technologies, USA) equipped with a 60 m ×0.25 mm × 0.25 μm DB5-MS column (Agi len tTechnologies, USA) coupled to a mass spectrometer (MS5975, Agilent, USA). The temperature programme was 80°C (1 min), 15 °C min−1 to 180 °C, 5 °C min−1 to 310 °C(20 min). The inlet temperature was 280 °C. The carrier gaswas He with a flow rate of 1.5 mL min−1. The temperature ofthe transfer line was 310 °C and 320 °C for the ion source. Theused regime was selected ion monitoring. PCBs and OCPswere analysed using a 7890 GC (Agilent Technologies,USA) coupled to Waters Quattro Micro GC (Waters, USA)equipped with SGE Analytical Science HT-8 (8% Ph) column(60 m × 0.5 mm × 0.25 μm, SGE Analytical Science,Australia) coupled with MS/MS (Agilent Technologies,USA). The temperature programme was 80 °C, 40 °C min−1

to 200 °C, 5 °C min−1 to 305 °C. The inlet temperature was280 °C. The carrier gas was helium with a flow rate of 1.5 mLmin−1. The temperature of the transfer line was 310 °C and ofthe ion source was 250 °C. The used regime was multiplereaction monitoring. The target compounds in this study were15 PAHs, acenaphthylene (ACY), acenaphthene (ACE),fluorene (FLN), phenanthrene (PHE), anthracene (ANT),fluoranthene (FLT), pyrene (PYR), benzo(a)anthracene(BAA), chrysene (CHR), benzo(b)fluoranthene (BBF),benzo(k)fluoranthene (BKF), BAP, indeno(1,2,3-cd)pyrene(IPY), dibenz(a,h)anthracene (DHA) and benzo(ghi)perylene(BPE); 6 PCBs, PCB28, PCB52, PCB101, PCB153, PCB138and PCB180; and 12 OCPs, namely 4 HCH isomers (α, β, γ,δ ) , 6 DDX compounds i .e . o ,p' - and p,p ’ -DDT,d i c h l o r o d i p h e n y l d i c h l o r o e t h e n e (DDE ) a n ddichlorodiphenyldichloroethane (DDD) and penta- and hexa-chlorobenzene (PeCB and HCB).

QA-QC

No field blanks were collected within this study, but two fieldblanks, each consisting of XAD and GFF, from a following,

Environ Sci Pollut Res (2019) 26:23429–23441 23431

methodologically identical study, were used instead. Theseblank levels of individual PAHs, PCBs and OCPs were belowthe limit of detection or low otherwise, suggesting minor con-tamination during sampling, transport and analysis. Meanblank values with standard deviations are provided inTable S2. There were also five solvent blanks analysed forPAHs and three solvent blanks for PCBs and OCPs, whichshowed levels below the detection limit except for PHE, FLT,PYR, α-HCH and γ-HCH, which had levels lower than theinstrumental limit of quantification (iLOQ). iLOQs were de-fined from the instruments as a signal to noise ratio of ten forthe lowest point of the calibration curve and are presented inTable S3.

The recoveries of individual samples were ranging from55.6 to 117.2% for PAHs and from 63.1 to 109.1% forPCBs and OCPs. The reported fluxes have not been adjustedfor recoveries but were blank corrected, by subtracting themean concentrations of SOCs in the field blanks. To thisend, blank values < iLOQ were replaced by 0. For derivationof temporal averages, values were replaced by iLOQ/2 when-ever the determined concentrations in samples were lowerthan iLOQ.

Results and discussion

Atmospheric bulk deposition flux of PAHs, PCBsand OCPs and their composition profiles

The total deposition fluxes for 15 PAHs (Σ15PAHs) total de-position fluxes ranged at 23 to 1100 ng m−2 d−1 with an aver-age value of 190 pg m−2 d−1 for all seasons and sites investi-gated (Table S4). The here found PAH deposition fluxes arecomparable with previous studies from remote or rural sites(i.e. 38–2000 ng m−2 d−1, see Table 1), but generally lowerthan those reported from urban sites (i.e. 36–20000 ng m−2

d−1, see Table 1). This is due to the stronger influence of PAHprimary sources (e.g. road traffic, fossil fuel burners forheating) in urban areas compared to remote or rural areas.PAHs have been effectively mitigated across Europe in recentdecades (EEA 2017). However, direct comparisons with otherstudies should be done with caution, given the different PAHsconsidered (in this study, N = 15 and in others N = 7–23).

In our study, FLT and PYR were generally the main con-tributors to PAHs’ deposition fluxes, accounting on averagefor 19% both (Fig. 1). There is one exception at KUCwhere insome samples (from autumn 2012 to summer 2013) BBF isalso a significant contributor accounting on average for 17%of the total flux of PAHs. The possible reason is because of thedifferent nature of this site, i.e. rural while all others are back-ground, which may reflect differences in emissions. Manyother studies also reported FLT and PYR as the main contrib-utors of ΣPAHs, with non-negligible contributions from PHE

and CHR (Birgül et al. 2011; Blanchard et al. 2007; Esen et al.2008; Fernández et al. 2003; Gambaro et al. 2009; Gocht et al.2007; Halsall et al. 1997; Ollivon et al. 2002; Rossini et al.2007).

For all seasons and sites investigated, total depositionfluxes for 6 PCBs (Σ6PCBs) and 12 OCPs (Σ12OCPs) mea-sured were 64–4400 (average value of 400 pg m−2 d−1) and410–7800 pgm−2 d−1 (average 1900 pgm−2 d−1), respectively(Table S4). These results are within the ranges spanned byother studies in Europe (Table 1). Bulk deposition of HCHwas reported up to one order of magnitude higher fromSwitzerland in the 1990s (Table 1), in accordance with emis-sion reductions achieved (EEA 2017). The results suggest thatatmospheric deposition in the 2010s is an important pathwayof pollution transfer to ecosystems in the Central Europeanbackground.

Wet deposition was expected to be most relevant for sub-stances partitioning to the particulate phase or gaseous, butwith significant water solubility. At KOS, a significant corre-lation (p < 0.05) between the total deposition mass flux andprecipitation amount is found only for the two HCH isomers.This test was applied only for the KOS data subset, because ofits size (N = 17, whileN = 4 orN = 8 for the other sites;N is thenumber of samples). The result supports the perception ofinfluence of water solubility/air-water equilibrium (see alsobelow, Henry coefficients of α- and γ-HCH are 0.7 and0.3 Pa m3 mol−1, respectively).

The deposition mass fluxes of PCBs were dominated byPCB153 (26%, Fig. 1). Next main contributors were PCB28,PCB138 and PCB180, depending on locations. This is inagreement with Agrell et al. (2002), but in contradiction withother studies in Europe which reported that PCBs depositionfluxes were dominated by lower molecular weight PCBs, spe-cifically PCB28, PCB52 and PCB101 (Bergknut et al. 2011;Carrera et al. 2002; Newton et al. 2014; Teil et al. 2004). Suchspatial variation of the substance pattern upon deposition isexpected as resulting from the spatial variability of precipita-t ion and tempera ture , the la t te r in f luencing al lintercompartmental processes (Stemmler and Lammel 2012;Wania et al. 2003; Wania and Westgate 2008).

The deposition fluxes of OCPs were generally dominatedby γ-HCH, accounting on average for 30% of Σ12OCPs, atCHU for even 52%. Second tomost contributedα-HCH to thedeposition flux of OCPs, accounting on average for 15%.From winter 2011/12 until winter 2013/14, HCH concentra-tion in air of KOS were 46% of the concentration of the DDTcompounds (Shahpoury et al. 2015), but the ratio of totaldeposition fluxes of these pollutants during this period wasFHCH/FDDX = 2.4. One decade earlier, HCH abundance inair at KOS was measured ≈ 50% higher than the one ofDDX, but more than one order of magnitude higher in rain-water collected in KOS (Holoubek et al. 2007). This compar-ison clearly points to a muchmore effective wet scavenging of


Table1

Overviewof

bulkdepositio

nfluxes

ofPA

Hs,OCPs

andPCBsreported

from

EuropeandtheMediterranean.

a Differentnumberof

congenersweremeasured.

bOnlyp,p’

isom

ersweremeasured

Site,yearof

sampling

Σ7PCB

(pgm

−2d−

1)

HCB(pgm

−2d−

1)

Σ4HCH

(ngm

−2d−

1)

Σ6DDX

(pgm

−2d−

1)

ΣnPAH(ngm

−2d−

1)

Type

ofsampler

Reference

a.Rem

ote

Sweden;1

996–2005

190–2300

0.7–11

(α+γ)

40–670

b20–390

(n=12)

Teflon-coatedsurface

Hansson

etal.2006

Andorra,N

orway,S

witzerland;1

997–1998

38–63

(n=23)

Stainlesssteelb

ucket

Fernándezetal.2003

Andorra,N

orway,S

witzerland;1

997–1998

1033–33,00

47–500

5–16

Stainlesssteelb

ucket

Carrera

etal.2002

Italy;

2003

553–18,217

Glass

bottle

Nizzetto

etal.2006

Austria,S

pain,S

cotland,S

lovakia;2004–2006

3733–16,267

33–400

0.6–2

(α+γ)

Teflon

orstainlesssteelreservoir

Arellano

etal.2015

Austria,G

ermany,Sw

itzerland;2

005–10

110–211

2–6

(α+γ)

395–1586

Isolated

funnel-adsorbersystem

Jakobi

etal.2015

Sweden;2

006–2009

570–10,000

Isolated


Bergknutetal.2011

Sweden;2

009–2010

2700–6333

0.5–4

(α+γ)

Isolated


New

tonetal.2014

Austria,C

zech

Republic,2011–2015

73–2030a

29–270

0.1–4

48–750

23–660

(n=15)

Isolated


Thisstudy

b.Rural

Sweden;1

989–1990

2300–4500

70–2700

1–40

(α+β+γ)

210–2000

(n=11)

Glass

collector

Brorström

-Lundénetal.1994

Baltic

sea;1990–1993

270–171,000

PUFplugs

Agrelletal.2002

Germany;

2001–2002

334–1063

(n=17)

Isolated


Gocht

etal.2007

Czech

Republic,2011–2013

64–4400a

47–230

0.3–2

490–5030

49–1100

(n=15)

Isolated


Thisstudy

c.Urban

UnitedKingdom

;1992–1992

1310–18,200

(n=13)

Glass

vessel

Halsalletal.1997

France;1

999–2000

177–2100

(n=14)

Aluminium

bottle

Ollivonetal.2002

France;1

999–2003

7671–12,0547

36–622

(n=14)

Aluminium

bottle

Blanchard

etal.2007

Italy;

2002–2004

221–10,575

(n=17)

Pyrexbottle

Rossini

etal.2007

Turkey;

2005

260–19,500

(n=15)

Stainlesssteelp

otEsenetal.2008

Italy;

2005

101–693

(n=15)

Stainlesssteelv

essel

Gam

baro

etal.2009

Turkey;

2006–2007

0.2–15

(β+γ)

11,600

(n=10)

Dry

andwetcollector

Binicietal.2014

Turkey;

2008–2009

63Stainlesssteelp

otCindorukandTasdem

ir2014

Italy;

2007–2008

92–2432

(n=7)

Glass

bottle

Amodio

etal.2014

Turkey;

2008–2009

11,400

(n=12)

Dry

andwetcollector

Birgületal.2011

Italy;

2015–2016

75–1220a

200–650

20–280

(n=20)

Isolated


Quetal.2019


HCH vs. DDT compounds, explained by the lower Henrycoefficient − 0.7 and 0.3 Pa m3 mol−1 for α- and γ-HCH,respectively, vs. 33 and 1.1 Pa m3 mol−1 for p,p’-DDE and -DDT, respectively (298 K; Jantunen and Bidleman 2006;Shen and Wania 2005; Xiao et al. 2004). Together with thecorrelation with precipitation amounts in KOS (above), it alsosupports the perception that the total deposition flux of OCPs

is dominated by wet deposition. A prevalence of γ-HCH andα-HCH among deposited OCPs had already been reportedand attributed to abundance in air, but also wet scavenging(Carrera et al. 2002; Newton et al. 2014; Cindoruk andTasdemir 2014; Jakobi et al. 2015). These results were con-sistent among the different sites, except for KUC where theflux of OCPs was dominated by p,p'-DDE accounting on

(a)

0%

20%

40%

60%

80%

100%

KOS KUC CHU WOL UNT GRU

ACY ACE FLN PHE ANT FLT PYR BAA

CHR BBF BKF BAP IPY DHA BPE(b)

0%

20%

40%

60%

80%

100%


PCB28 PCB52 PCB101 PCB153 PCB138 PCB180

(c)

0%

20%

40%

60%

80%

100%


PeCB HCB α-HCH β-HCH γ-HCH δ-HCHo,p'-DDE p,p'-DDE o,p'-DDD p,p'-DDD o,p'-DDT p,p'-DDT

Fig. 1 a PAH, b PCB and c OCPpatterns across sites


average for 31%. This may reflect the different land use of thepast, given that DDTwas used for agricultural purposes in thisregion of the Czech Republic until the 1970s.

Seasonal and spatial variations

Significantly (p < 0.05) higher PAH deposition fluxes wereobserved at KUC than at the other sites. The spatial variationacross the other sites, apart from KUC, was lower for PAHsthan for PCBs. The maximum at the rural site KUC was ex-pected, because of local emissions, namely domestic heatingfrom a nearby village with road traffic and agricultural ma-chinery, unlike at the other sites. The PAH deposition flux atKUC site ranged from 49 to 1100 ng m−2 d−1 with an averageof 140 ngm−2 d−1, i.e. 2–6 times higher than for the other sites(Fig. 2, Table S4). The highest flux of PAHs at KUC wasobserved in spring-summer, while at KOS, it was highest inautumn–winter and at WOL it was highest in summer. Theseresults are somewhat unexpected, because the concentrationof PAHs in the air are higher in winter everywhere (Dat andChang 2017), which results from the combination of severalfactors i.e. increased sources (i.e. domestic heating), meteoro-logical conditions (i.e. lower height of mixed layer; Finlayson-Pitts and Pitts 2000; Dvorská et al. 2012) and longer photo-chemical lifetime (Finlayson-Pitts and Pitts 2000; Dvorskáet al. 2012). Obviously, the seasonal variations of PAH bulkdeposition is not dominated by atmospheric concentrationthroughout the region, but influenced by other, spatially vari-able factors, such as meteorological. Also, earlier studies(Dickhut and Gustafson 1995; Fernández et al. 2003) ex-plained the seasonality of the bulk deposition flux by the sea-sonality of precipitation. In the here studied region, highestprecipitation was generally observed in summer (Table S1).Most of the studies (Halsall et al. 1997; Ollivon et al. 2002;Blanchard et al. 2007; Gocht et al. 2007; Esen et al. 2008;Birgül et al. 2011; Binici et al. 2014) reported highest levelsof PAHs flux in winter. Moreover, we note that the influenceof open fires on the PAH time series cannot be excluded.

The PAH bulk deposition time series in KOS, ≈4 years,does not show a downward trend (Table S4, Fig. 2). A down-ward trend could reflect and would eventually confirm ongo-ing mitigation measures (EEA 2017). Because of interannualvariation of precipitation and other environmental parameters,much longer time series would be needed to identify a signif-icant long-term trend.

Significantly (p < 0.05) higher deposition flux of Σ6PCBwas found at KUC, where it ranged from 64 to 4400 pg m−2

d−1 with an average of 140 pg m−2 d−1, i.e. which is 1.4–4.5times higher than for the other sites (Table S4). This wasexpected because of the rather intense historical use of PCBsin this region (electrical equipment and constructions;Christan and Janse 2005). Regarding the seasonal variations,a higher flux of Σ6PCBs was generally measured in summer

in KOS, KUC and WOL, while the lowest mass flux to allsites was generally measured in autumn. At the other sites, noobvious seasonal variation was found. There is a peak in sum-mer 2012 in KOS. The possible reason is the construction of ameteorological tower at the observatory, distanced of about100 m from the sampling site that may have enhancedrevolatilisation from soils. PCB deposition fluxes were report-ed with varying seasonality from sites across Europe(Brorström-Lundén et al. 1994; Agrell et al. 2002; Carreraet al. 2002; Teil et al. 2004; Nizzetto et al. 2006; Blanchardet al. 2007; Bergknut et al. 2011; Newton et al. 2014).

The total deposition fluxes for Σ12OCPs observed for thedifferent sites (Fig. 2, Table S4) were not statistically differentfrom each other. This supports the perception of long-lived(persistent), regionally distributed pollutants. However, therewas one exception, namely PeCB was much higher at theAustrian sites (averages ranging 110–250 pg m−2 d−1) thanat the Czech sites (averages ranging 12–29 pg m−2 d−1, sametime period; Fig. 1c). The reason is unknown.

The highest flux of Σ12OCPs was generally measured insummer, but without significant seasonal variation. Jakobiet al. (2015) reported higher deposition fluxes in summer forHCB and HCH in Central Europe, but obvious differencesacross sites for DDX compounds, similar to this study. Thevariability was attributed to different origin of air massesadvected to the sites. Arellano et al. (2015) also reportedhigher flux of HCH in spring–summer in Slovakia. Newtonet al. (2014) did not find an obvious seasonal variation.

The ratio α-HCH/γ-HCH was not significantly differentacross sites (p < 0.05) and smaller than 1 in all seasons at allsites. This suggests using lindane rather than technical HCH.The fraction of 5 ring PAHs among all measured PAHs wasnot significantly different (p < 0.05) across sites with oneexception, comparing GRU and WOL. These two ratios sug-gest that pollutants are distributed equally in Central Europe.The ratio between sum of all DDT isomers over all isomers ofDDX compounds was significantly different (p < 0.05) be-tween KOS and all other sites with one exception, GRU.This ratio was highest at KOS, suggesting most recent usageof DDT in that area. The ratio between o,p isomers and allisomers of DDX compounds was significantly different (p <0.05) between KOS and all sites, also, between KUC andCHU, GRU and then between UNT and GRU. These resultsmust be viewed with caution for the Austrian sites, because ofthe low number (N = 4) of samples.

Distribution between XAD and GFF

The sampler used was designed such that the freely dissolvedphase was collected on XAD while the particulate phase wascollected on GFF. Therefore, the fraction observed on GFFwill be described using the particulate fraction from deposi-tion (θdep), which should not be confused with the particulate


mass fraction in aerosols (θ). It is known that for apolar ormid-polar compounds particle, scavenging is more efficientthan gas scavenging (Bidleman 1988); therefore, we can

expect that θdep will be higher than θ. However, we cannotexclude sampling artefacts affecting the accuracy of θdep, asdiscussed above (BMaterial and methods^).

(a)

(b)

(c)

1

10

100

1000

10000

Fb

ulk

(ng d

ay-1

m-2

)


1

10

100

1000

10000

Fb

ulk

(ng d

ay-1

m-2

)


1

10

100

1000

10000

Fb

ulk

(ng d

ay-1

m-2

)


Fig. 2 Bulk deposition fluxes of a 15 PAHs, b 6 PCBs and c 12 OCPs shown in log axis


(a)

(b)

(c)

3042 41 37

49 47 4858 53 59 61 62

70 64 69

7058 59 63

51 53 5242 47 41 39 38

30 36 31

0%

20%

40%

60%

80%

100%

ACY ACE FLN PHE ANT FLT PYR BAA CHR BBF BKF BAP IPY DHA BPE

GFF XAD

30 3856 60

73 74

70 6244 40

27 26

0%

20%

40%

60%

80%

100%

PCB28 PCB52 PCB101 PCB153 PCB138 PCB180

GFF XAD

36 26 15 15 15 18 2555 55 48 57 59

64 74 85 85 85 82 7545 45 52 43 41

0%

20%

40%

60%

80%

100%

GFF XADFig. 3 Average distribution between GFF and XAD of a PAHs, b PCBs and c OCPs


Only measurements for which SOCs were > iLOQ in bothGFF and XAD are considered. For PAHs and PCBs, θdepgenerally increased with increasing molecular weight and/ordecreasing volatility (Fig. 3). However, this was not observedfor OCPs (Fig. 3). Moreover, θdep was generally higher insummer than in winter for all groups of compounds(Figure S3). This implies that the particulate mass fraction inaerosols, θ, which shows the opposite seasonality (e.g. forPAHs and OCPs in the study region: Shahpoury et al. 2015;Degrendele et al. 2014), is not preserved in total deposition.The same shift was already reported for wet deposition fluxesfrom KOS (Škrdlíková et al. 2011). The seasonal variations ofcloud depth and cloud base height, and of the scavengingefficiencies of rain and snow for gases and particles(Bidleman 1988; Škrdlíková et al. 2011; Wania andWestgate 2008), as well as of wind velocity, influencing dryparticle deposition (Pryor et al. 2007), may well explain thefinding.

Apart from environmental parameters, sampling artefactssuch as temperature-driven volatilisation from the surface ofthe sampler, stronger in summer, could have shifted θdep asobserved. Also, less precipitation in winter (Table S1) mayhave caused a negative sampling artefact (i.e. collected partic-ulate material not efficiently washed from the surface of thesampler to the sampling media), eventually contributed toshifted θdep as observed.

Conclusions

We studied atmospheric bulk deposition of a number of or-ganic pollutants at 6 sites in Central Europe during 2011–2015. The time series (1–≈ 4 years) are too short, to addresslong-term trends. The results suggest that atmospheric depo-sition in 2010 is an important pathway of pollution transfer toecosystems in the Central European background. The sub-stance patterns are quite similar across sites (except for one,the rural site, which is explained by historical usage/pollutionof HCH and DDT; and except relatively higher PeCB deposi-tion at the Austrian sites).

For substances which deposition is dominated by dry par-ticle deposition, and because of the significance of surfaceroughness for dry particle deposition (McLachlan andHorstmann 1998; Pryor et al. 2007; Glüge et al. 2015), theobserved patterns may deviate significantly from the sub-stance patterns the natural surfaces (grassland, cropland, for-est) are subject to. This also implies a systematic underesti-mate of the flux of those pollutants which mostly partition toparticulate matter in ambient aerosols. For this reason andbecause of the negative sampling artefact arising fromvolatilisation losses of dry deposited gaseous substances fromthe sampler surface, fluxes derived from bulk deposition sam-plers in use should be understood as lower estimates of the

flux into terrestrial ecosystems. This underestimate is signifi-cant as dry deposition is more efficient than wet deposition forPAHs (Škrdlíková et al. 2011) and, considering substanceproperties (Koa, besides other; Wania and Westgate 2008),even more so for PCBs and OCPs. While the volatilisationlosses might be unavoidable for long sampling periods, thedry particle deposition efficiency could be mimicked morerealistic by a sampler design with higher surface roughness,e.g. mimicking the surface roughness of particularly forest,but also cropland or grassland. Similarly, deposition to stonefaçades had been mimicked using a sampler surface with theidentical roughness as the façade under study (Lammel andMetzig 1997).

Acknowledgements Open access funding provided by Max PlanckSociety. We thank Ondřej Sáňka for help with geographical visualisation.

Funding information This work was funded by the EuropeanCommission through the Territorial Cooperation Programme Austria–Czech Republic 2007–2013 (MonAirNet project, No. M00124), theMinistry of Education, Youth and Sports of the Czech Republic throughResearch Infrastructure (project LM2015051) and ACTRIS-CZ(LM2015037 and CZ.02.1.01/0.0/0.0/16_013/0001315) and by theCzech Science Foundation (GAČR 503 16-11537S).

Compliance with ethical standards

Conflict of interest The authors declare that they have no conflict ofinterest.

Open Access This article is distributed under the terms of the CreativeCommons At t r ibut ion 4 .0 In te rna t ional License (h t tp : / /creativecommons.org/licenses/by/4.0/), which permits unrestricted use,distribution, and reproduction in any medium, provided you giveappropriate credit to the original author(s) and the source, provide a linkto the Creative Commons license, and indicate if changes were made.

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Bulk atmospheric deposition of persistent organic pollutants and polycyclic aromatic hydrocarbons in Central EuropeAbstractIntroductionMaterial and methodsSamplingSample preparation and analysisQA-QC

Results and discussionAtmospheric bulk deposition flux of PAHs, PCBs and OCPs and their composition profilesSeasonal and spatial variationsDistribution between XAD and GFF

ConclusionsReferences